Photographic material

ABSTRACT

A photographic material, comprising a support with a mixture applied thereto, said mixture comprising an organic dye such as methylene blue or thionine blue, a water-soluble salt of silver, gold, platinum or palladium and disodium salt or ethylenediaminetetraacetic acid or triethanolamine. The content of said components in said mixture is the following (g per m2 of the support surface area): ORGANIC DYE5.10 3-5.10 2 WATER-SOLUBLE SALT OF SILVER,GOLD, PLATINUM OR PALLADIUM1.10 3-5.10 2DISODIUM SALT OF ETHYLENEDIAMINE TETRAACETIC ACID ORTRIETHANOLAMINE2.5-20 Said mixture may also comprise gelatine or polyvinyl alcohol in an amount of 2-50 g per m2 of the support surface area. The photographic material according to the invention exhibits light sensitivity both in ultraviolet and visible regions of the spectrum. This permits to use this photographic material to produce negative and positive images when taking photographs and reproducing coloured objects.

United States Patent Titov et al.

[ Aug. 21, 1973 PHOTOGRAPHIC MATERIAL [76] Inventors: Alexei AlexeevichTitov, ulitsa Gatvalda 18a, KV. 65 Jury Vasilievich Smirnov, poselvkMoskvorechie 48,

KV. 48; Jury Shabsaevich Mashkovsky, Zubovsky bulvar 16/20, KV. 2, all

of Moscow {Ernest Dmitriefidh Tamitsky, Push kinsky raion, stantsiaMamontovka, ulitsa Oktyabrskay a,

22, Moskovskay a oblast; Vladimir NikitoviclrChursin, ulitsa Gari baldi7, KV. 5, mose'swg Ljiidinila Leonidovna Antonova, stavtsia Podlipki,proezd Makarevko, 8,

KV. 18, Moskovskaya oblast; Tamara Stepanovna Selitskaya, KrasnyStroitel, 2 Kvartal, l, KV. 31, Moscow, all of U.S.S.R.

Filed: Feb. 3, 1972 Appl. No.: 223,338

[52] US. Cl 96/88, 96/92, 96/94,

96/1 14.6 Int. Cl G03c l/00 Field of Search 96/88, 114.6, 94,

[56] References Cited UNITED STATES PATENTS 3,658,534 4/1972 lshitani etal. 96/88 R Primary Examiner-Norman G. Torchin AssistantExaminer--Richard L. Schilling Attorney-Eric H. Waters et a].

organic dye 5-l0 -5l0' water-soluble salt of silver,

gold, platinum or palladium l-l0-S-l0 disodium salt of ethylenediaminetetraacetic acid or triethanolamine 2.5-20

Said mixture may also comprise gelatine or polyvinyl alcohol in anamount of 2-50 g per m of the support surface area.

The photographic material according to the invention exhibits lightsensitivity both in ultraviolet and visible regions of the spectrum.This permits to use this photographic material to produce negative andpositive images when taking photographs and reproducing colouredobjects.

3 Claims, No Drawings PHOTOGRAPHIC MATERIAL The present inventionrelates to a photographic material which is light-sensitive both inultraviolet and visible regions of the spectrum. Such a material may beused in conventional and scientific photography, cinematography, inmaking microfilms and in documents duplication, as well as in printing.

Known in the art is a photographic material, comprising a support with amixture of a light-sensitive material such as a trivalent iron salt, anda salt of a noble metal, such as palladium, applied thereto.

This prior-art photographic material exhibited very low lightsensitivity and was sensitive only to the ultraviolet region of thespectrum. For this reason, commercial application of this photographicmaterial was very limited, since it must be used with specialultraviolet light sources, very long exposure and highly expensivequartz optical systems. Furthermore, a restricted range of spectralsensitivity makes this photographic material absolutely unsuitable fortaking photographs (that is, this photographic material cannot be usedas negative material).

It is an object of the present invention to provide a photographicmaterial which is light-sensitive both in ultraviolet and visibleregions of the spectrum.

In accordance with this and other objects, the invention consists in theprovision of a photographic material, comprising a support with amixture applied thereto, said mixture comprising an organic dye, such asmethylene blue or thionine blue, a water-soluble salt of silver, gold,platinum or palladium and disodium salt of ethylenediamine-tetraaceticacid or triethanolamine, said mixture containing the followingquantities of said components (g per m of the support surface area):

organic dye 5-10'= 5-10" water-soluble salt of silver,

gold, platinum or palladium H0- 510" disodium salt ofethylenediaminetetraacetic acid or triethanolamine 2.5

The photographic material according to the invention is sensitive bothin ultraviolet and visible regions of the spectrum, whereby it may beused to obtain negative and positive images in reproducing colourobjects.

In the material according to the invention a visible image is built upby a conventional method of physical development of latent image centersconsisting in reducing ions of a cheap metal, such as copper, mercury,nickel on said centers. This results in a considerable reduction of theconsumption of an expensive metal, such as silver, which takes placewhen silver halide photographic materials are used. in order to producehalftone photographic images having fine grains, it is desirable to usea photographic material comprising 2-50 g per m' of the support surfacearea of gelatine or polyvinyl alcohol.

In order to increase the quantum yield of photochemical reaction, andhence to increase light sensitivity of the photographic materialaccording to the invention, a water-soluble salt of bivalent copper,trivalent iron or tetravalent tin in an amount of 1-10 510 g per in ofthe support surface area is introduced into the material.

The photographic material according to the invention is prepared in thefollowing manner.

Aqueous solutions of each of the above-said components having apredetermined concentration are prepared and then mixed in apredetermined ratio in darkness or when exposed to the light of anincandescent lamp screened with a blue filter.

When preparing the photographic material to be used in making linecopies of documents, a paper support is impregnated with the mixture ofthe components thus prepared (without introducing gelatine and polyvinylalcohol).

When preparing the photographic material to be used for high-gradehalf-tone images, the mixture of components thus prepared (includingalso gelatine or polyvinyl alcohol) is appliedto a support (paper,triacetyl cellulose, glass) to produce a uniform layer using 1 l of anaqueous solution per rn of the support surface.

impregnated paper support or light-sensitive layer applied to thesupport is dried at 20-60C.

Exposure of the photographic material thus prepared is made in daylightor in the light of an incandescent lamp (without a filter or through anorange or red filter, if necessary) during 0.5 to 5 minutes with theillumination of the lightsensitive layer of -500 luxes.

Upon the exposure the material is soaked for 10-15 minutes in water or,which is better, in a slightly acidic solution in order to preventreversible (dark) reaction and eliminate the unreacted substancesinterfering with the development. After the soaking all operations withthe exposed material are performed in any light.

The exposed material is developed with a physical developer. Knownphysical developers may be used, such as mercury, copper, nickeldeveloper and the like. The development is performed at room temperaturefor 0.1 to 1 hour.

Upon the physical development, the photographic material is washed withrunning water during l0-20 minutes and is then dried in air or in dryingapparatus at 40-80C.

The photographic material according to the invention may be used inmaking line copies of documents, negative and positive half-tonepictures, in taking photographs and in making reproductions of colouredobjects.

Better understanding of the present invention may be had from thefollowing examples illustrating the preparation and application of thephotographic materialaccording to the invention.

EXAMPLE l An aqueous solution of the following composition (g/l) wasprepared:

methylene blue 5'10" disodium salt of ethylenediaminetetraacetic acid 20silver nitrate S10" The pH of the solution was of 4.5 5.5.

In order to prepare this solution, aqueous solutions of each of theabove-mentioned components were first separately prepared in any light.Then these solutions were mixed in the light of an incandescent lamp of25 W screened with a blue filter, which was placed at a distance of l mfrom the working zone.

The resulting light-sensitive solution was used for impregnating a papersupport by applying 400 ml of the solution per in of the supportsurface. The impregnation was effected at room temperature and in theabove-mentioned non-actinic light. Then the support was dried in air for1 hour.

The resulting photographic material comprised a support of pale bluecolour impregnated with the lightsensitive composition. This materialwas sensitive substantially to yellow and red regions of the spectrum.

The photographic material thus prepared was used to produce positivecopies from negative line pictures (texts, documents drawings). Thephotographic material was exposed during minutes through a negative by acontact method in the light of an incandescent lamp of 500 W placed at adistance of l m.

Upon the exposure, the material was soaked in water for IO-l5 minutes.This operation was performed in the above-said non-actinic light. Afterthe soaking, the material exhibited no light sensitivity, and itsfurther treatment (physical development, washing and drying) was done inany light.

Visible image was obtained by means of physical development of thelatent image using mercury physical developer. In order to prepare thisdeveloper, two aqueous solutions of the following composition (g/l) werefirst prepared:

Solution l Mercury nitrate 8.35 Potassium bromide 8.0 Crystalline sodiumsulphite 120 Solution ll Metol 20 Crystalline sodium sulphite 40 maximumdensity, D 1.4 minimum density. D... 0.3 0.07

fog density, D

The image was built up with contrasting black lines.

EXAMPLE 2 An aqueous solution of the following composition (g/l) wasprepared:

methylene blue 510' triethanolamine 20 silver nitrate 110 coppersulphate 2.510"

The pH of the solution was of l0-l l.

The preparation of the light-sensitive solution, its application to apaper support, exposure and treatment of the exposed photographicmaterial were performed similarly to Example I.

The resulting line positive image exhibited the same charateristics asin Example 1.

EXAMPLE 3 An aqueous solution of the following composition (g/l) wasprepared:

gelatin: 50

4 methylene blue 8-l0" disodium salt of ethylenediaminetetraacetic acid9.3 silver nitrate 310 The pH of the solution was 4.5 5.5.

The solution was prepared according to Example 1. Then the solution wasapplied at 40C and in nonactinic light, to produce a uniform layer, to asupport of cellulose triacetate, using 1 l of the solution per m of thesupport surface. Upon the application of the light-sensitive solution tothe support it was cooled at 3-5C for 1 minute and then dried at 40Cduring 30 minutes.

When viewed in a passinglight, the resulting photographic material wastransparent (there was no turbidity) due to homogeneous structure of thelayer.

The photographic material was used to produce halftone negative images.In doing this, the photographic material was exposed for 1 minute in thelight of an incandescent lamp of 500 W placed at a distance of l m.

Upon the exposure, the photographic material was soaked as described inExample 1, after which it exhibited no light sensitivity. Furthertreatment of the material (physical development, washing and drying) wasperformed in any light.

A latent image was developed by means of a mercury physical developersimilar to that described in Example 1. The development was effected at25C for 30 minutes.

Upon the development, the photographic material was washed in runningwater during 20 minutes and dried in air for one hour.

The resulting half-tone image exhibited the following characteristics:

maximum density, D minimum density, D... fog density, D, O

An aqueous solution of the following composition (g/l) was prepared:

gelatine 50 methylene blue l-l0' disodium salt ofethylenediaminetetraacetic acid 9 ferrous sulphate (oxy-salt) 4J0 silvernitrate L710" The pH of the solution was of 4.5 5.5. V The solution wasprepared as described in Example I. Then the solution was applied to apaper support at 40C and in non-actinic light to produce a uniform layerusing 1 l of the solution per m of the support surface. Upon theapplication of the light-sensitive solution to the support it was cooledat 3-5C for 1 minute and dried at 40C during 30 minutes.

The resulting photographic material was used to produce half-tonepositive images. in doing this, the photographic material was exposedduring 40 seconds through a negative by a contact method in the light ofan incandescent lamp of 500 W placed at a distance of l m.

Upon the exposure, the material was soaked in a 0.1 percent aqueoussolution of sulphuric acid, after which the material exhibited no lightsensitivity.

Visible image was obtained by means of the development of the latentimage using a physical developer. In order to prepare this developer,two aqueous solutions were first prepared. Solution 1 had the followingcomposition:

crystalline copper sulphate 7 potassium tartrate 22 sodium hydroxide 4.5

Solution ll was a 1 percent aqueous solution of formaldehyde. Before thedevelopment, solutions I and I] were mixed in a volumetric ratio of l:l.The pH of the developer was 10-1 1. The development was performed at 25Cfor l minutes using 1 l of the developer per in of the exposedphotographic material.

Upon the development, the photographic material was washed with runningwater for 20 minutes and dried in air during one hour.

The resulting half-tone image exhibited the following characteristics:

maximum density, D l.0 minimum density, D, 0.09 fog density, D, 0.08

The photographic image was built up with progressive change of densityfrom D,,,,, to D,,,,,, and was of brown colour.

EXAMPLE 5 An aqueous solution of the following composition (g/l) wasprepared:

gelatine 30 methylene blue 8-l0 triethanolamine 5 copper sulphate H0silver sulphate 5 10" The pH of the solutionwas 10-1 1.

The solution was prepared similarly to that of Example 1. Then thesolution was applied to a glass support at 40C and in non-actinic lightto produce a uniform layer using 1 l of the solution per m of thesupport surface. Upon the application of the light-sensitive solution tothe support, it was cooled at 3-5C for 1 minute and dried at 40C during30 minutes.

The resulting photographic material was used to produce half-tonepositive images, the conditions of exposure and further treatment of thephotographic material being similar to those described in Example I.

The resulting half-tone image exhibited the following characteristics:

maximum density, D 1.3 minimum density, D, 0.08 fog density, 0, 0.05

The photographic image was built up with progressive change of densityfrom D, to D, and was of black colour.

EXAMPLE 6 An aqueous solution of the following composition (g/l) wasprepared:

gelatine 50 methylene blue 9-10 disodium salt ofethylene-diaminetetraacetic acid 20 tetravalent tin nitrate 5-l0tetravalent gold chloride 4 10" The pH of the solution was of 4.5 5.5.

The preparation of the light-sensitive solution, its application to apaper support and the treatment of the material upon the exposure wereperformed as described in Example 4.

The photographic image was built up with progressive change of densityfrom D to D,,,,,, and was of brown colour.

EXAMPLE 7 An aqueous solution of the following composition (g/l) wasprepared:

polyvinyl alcohol methylene blue 810' disodium salt ofethylene-diaminetetraacetic acid 9.3 tetravalent tin chloride 4H0tetravalent platinum chloride H0 The pH of the solution was of 4.5 5.5.

The preparation of the light-sensitive solution and its application to apaper support were performed as described in Example 4.

The resulting photographic material was used to produce half-tonepositive images. In doing this, the photographic material was exposedduring 1 minute through a negative by a contact method in the light ofan incandescent lamp of 500 W placed at a distance of l m.

The exposed material was then soaked in water for 10-15 minutes, aferwhich the material exhibited no light sensitivity.

Visible image was obtained by means of physical development, using anickel physicall'developer. ln order to prepare this developer twoaqueous solutions were first prepared. Solution I had the followingcomposition 7 nickel sulphate 23 potassium citrate 32,4

Solution ll comprised an aqueous solution of sodium hypophosphite with aconcentration of 240 g/l. Before the development solutions I and ll weremixed in a volumetric ratio of 4:1 respectively. The pH of the developerwas l0-ll.

Upon the exposure, the photographic material was developed during 15minutes at C using 1 l of the developer per 5 m of the photographicmaterial surface area.

Upon the development, the photographic material was washed in runningwater for 25 minutes and dried in air for one hour.

The resulting half-tone image exhibited the following characteristics:

maximum density, D 1.8 minimum density, D... 0.l fog density, D, p 0.09

The photographic image was built up with progressive change of densityfrom D to D,,,,,, and was of black colour.

EXAMPLE 8 An aqueous solution of the following Composition (2") asprepared:

polyvinyl alcohol 20 methylene blue 510" disodium salt ofethylenediaminetetraacetic acid 2.5 3 10" copper chloride palladiumsulphate The pH of the solution was 4.5 5.5.

The preparation of the light sensitive solution, its application to apaper support, exposure and treatment of the exposed material wereperformed as described in Example 7.

The resulting half-tone positive image was built up with progressivechange of density from D,,,,,, to D,,,,,, and was of dark colour.

EXAMPLE 9 An aqueous solution of the following composition (g/l) wasprepared:

polyvinyl alcohol 25 methylene blue -10' disodium salt ofethylenediaminetetraacetic acid 10 copper sulphate 510" tetravalentplatinum chloride H0 The pH of the solution was 4.5 5.5.

The preparation of the light sensitive solution was performed asdescribed in Example 1. Then the solution was applied to a glass supportat 40C and in non actinic light to produce a uniform layer using 1 l ofthe solution per rn of the support. Upon the application of thelight-sensitive solution to the support, it was cooled at 35C for 1minute and dried at 40C during 30 minutes.

The resulting photographic material was used to produce half-tonenegative images. In doing this, the material was exposed during oneminute in the light of an incandescent lamp of 500 W placed at adistance of l m. Upon the exposure, the material was soaked in water,developed in a physical developer, washed in running water and dried asdescribed in Example 7.

The resulting negative photographic image exhibited the followingcharacteristics:

maximum density, D, 2.5 minimum density. D... 0.1 fog density. D. 0.07

The photographic image was built up with progressive change of densityfrom D to D,,,,,, and was of black colour.

EXAMPLE 10 An aqueous solution of the following composition (g/l) wasprepared:

gelatine thionine blue S-IO" disodium salt of ethylenediaminetetraacetic acid 20 ferrous sulphate (oxy-salt) 410" silver nitrate 2'l0 The pH of the solution was 4.5 5.5.

The preparation of the light-sensitive solution, its application to apaper support, exposure and treatment of the exposed photographicmaterial were performed according to Example 1.

The resulting line positive image exhibited the followingcharacteristics:

maximum density, D... minimum density, -ln fog density, D,

The photographic image was built up with contrasting lines having blackcolour.

We claim:

l. A photographic material, comprising a support with a mixture appliedthereto, said mixture comprising an organic dye, selected from the groupconsisting of methylene blue and thionine blue, a water-soluble salt ofa metal selected from the group consisting of silver, gold, platinum andpalladium, and an amino-compound selected from the group consisting ofdisodium salt of ethylenediaminetetraacetic acid and triethanolamine,the content of said components in said mixture being the following (gper in of the support surface area):

organic dye 510" 5-10" watersolublc salt of one of said noble metals1'10 510" amino-compound 2.5 20

face area.

a a: t a a

2. A photographic material according to claim 1, wherein said mixturealso comprises a binder selected from the group consisting of gelatineand polyvinyl alcohol in an amount of 2-50 g per m2 of a support surfacearea.
 3. A photographic material according to claim 1, wherein saidmixture further comprises a water-soluble salt of a metal selected fromthe group consisting of bivalent copper, trivalent iron and tetravalenttin in an amount of 1.10 2 - 5.10 1 g per m2 of the support surfacearea.